# Introduction Arrhenius Law Collision Theory Transition State Theory

TEMPERATURE DEPENDENT TERM

Temperature Dependent Term

Temperature dependent terms that have been developed:

Arrhenius Law
Collision Theory

Transition State Theory

Temperature Dependent Term

Arrhenius, a Swedish Chemist, proposed that the temperature dependence of the reaction rate constant, kA, could be correlated by an equation:
◦ ko = frequency factor or pre-exponential factor ◦ E = activation energy (J/mol or cal/mol) ◦ R = gas constant ◦ T = absolute temperature

Temperature Dependent Term  Activation Energy ◦ Minimum energy that must be possessed by reacting molecules before the reaction will occur ◦ Difference between average energy of those molecules that do react and the average energy of all molecules ◦ Just an empirical parameter relating the reaction rate constant to temperature = fraction of the collisions between molecules that attain the activation energy .

first linearize the Arrhenius Equation .Temperature Dependent Term  Experimental Determination of E ◦ The activation energy can be determined experimentally by carrying out the reaction at several different temperatures and determining the rate constants. at these temperatures. kA. ◦ To determine E.

Temperature Dependent Term .

Temperature Dependent Term  Features of Arrhenuis equation (Levenspiel) ◦ A plot of k vs 1/T gives a straight line. reactions with low activation energies are relatively temperature-insensitive. small slope for small E. with a large slope for large E. ◦ Reactions with high activation energies are very temperature sensitive. .

Temperature Dependent Term (Levenspiel) .

Temperature Dependent Term  Collision Theory ◦ Originally based on the kinetic theory of gases ◦ “reaction” occurs when:  Molecules collide  Possess enough energy to undergo transformation Rate of reaction = (frequency of collision) x (fraction of collisions that have energy to react) .

respectively.Temperature Dependent Term  How to derive the frequency of collision? ◦ Consider: ◦ A and B are rigid spheres of radii σA and σB. ◦ A moves at a relative velocity UR. σB σB σA UR σB .

Temperature Dependent Term  Collision is assumed when A “touches” B. σB σA . with a collision radius (σAB =σA and σB) within a collision area S =π(σA and σ B ) 2.

equal to:  σAB σA UR A .Temperature Dependent Term Distance traveled by molecule A = URΔt  At time Δt. A sweeps a volume V.

Temperature Dependent Term   While A sweeps out this volume. Number of collisions is: σAB σA σB A UR σB σB . it will undergo collisions with B within this volume.

Temperature Dependent Term  From kinetic theory of gases: ◦ Where:  Therefore. the frequency of collision of all molecules A is: .

Temperature Dependent Term  Rate of reaction (with respect to number of molecules reacting) = (frequency of collision) x (fraction of collisions that have energy to react)  Using Avogadro’s number: .

Temperature Dependent Term .

or revert back to reactants. ◦ Schematic representation: .Temperature Dependent Term  Transition State Theory ◦ Reactants combine to form unstable intermediates called “ activated complexes”. which decompose to products spontaneously.

QA.Temperature Dependent Term  Final form of reaction rate: ◦ ◦ ◦ ◦ K’ =Boltzman constant H = Planck constant QABC.QB = partition functions per unit volume Eo = energy change going from reactants to products .

thus. the variation due to Tm term is masked.Temperature Dependent Term Arrhenius Law Collision Theory Transition State Theory  The fraction of collision term is more sensitive than the Tm term. .

Introduction Intermediates Reaction Schemes Testing of Mechanisms and Models Examples of Reaction Mechanisms KINETIC MODELS .

which cannot be measured or observed as they are in very minute quantities.  .Kinetic Models Kinetics of non-elementary reactions are explained using the following assumption:  The overall reaction of a nonelementary reaction can be written as a sequence of elementary reactions (reaction mechanism).  The sequence may postulate the appearance of intermediates.

.Kinetic Models Reaction mechanism/ kinetic model  The “*” represents unobserved intermediates.

INTERMEDIATES AND REACTION SCHEMES .

Kinetic Models Intermediates  Types of intermediates which may be postulated in a reaction mechanism: Free Radicals Contains an unpaired electron Ion or Polar Substances Electrically charged atoms or molecules Molecules Transition Complexes Short life span Unstable forms of molecules having strained bonds or unstable associations which either decompose to give products or return to molecules in the normal state .

Kinetic Models Reaction Schemes  Non-chain reactions  Chain Reactions ◦ Generally consists of sequences  Initiation  Active intermediate initially formed  Propagation  Active intermediate is propagated (increased formation) with simultaneous product formation  Termination  Active intermediate is destroyed by transformation into more stable products .

Kinetic Models   Initiation Propagation*  Termination propagation is an essential feature Intermediate is not consumed but acts as a catalyst *the • .

EXAMPLES OF REACTION MECHANISMS .

Kinetic Models  The Kinetic Model/Reaction mechanism can be expressed/ named from the type of intermediate and reaction scheme ◦ Non-chain reactions  Molecules  Transition Complexes ◦ Chain reactions  Free radicals .

Chain Reaction Mechanism: .Kinetic Models  Free Radical.

Kinetic Models  Molecular Intermediate. Non-chain Reaction Mechanism .

Non-chain Reaction Mechanism: H2 + I2 ↔ H I ↔ 2HI H I H I H I .Kinetic Models  Transition Complex.

TESTING OF POSTULATED REACTION MECHANISM .

Kinetic Models Given a reaction and experimental rate law which is not elementary.  . we can attempt to propose a reaction mechanism to explain the nonelementary algebraic expression of the rate law.  To check if the proposed reaction mechanism is correct. the theoretical rate law must be similar to the experimental rate law.

.Kinetic Models How? Answer:  Obtain the theoretical rate laws from the proposed reaction mechanism and apply the steady-state approximation.

4. Apply the steady state approximation. 2. set-up the elementary rate law of the target component (reaction product or reactant) rA = will include expressions involving concentrations of intermediates. From the reaction mechanism. . 3. Compare the derived/ theoretical rate law with the experimental rate law. If analogous. the postulated reaction mechanism is correct.Kinetic Models 1. Substitute CI back to the rate law obtained in (1). and simplify.

Kinetic Models  Consider: .

Kinetic Models  Use Rules-of-thumb: .

Kinetic Models  Proposal: .